Antiperspirant and deodorant sticks containing triglyceride gellants having improved high temperature texture and phase stability

ABSTRACT

Disclosed are anhydrous antiperspirant and deodorant compositions comprising from about 0.1% to about 50% by weight of an antiperspirant or deodorant active; from about 10% to about 90% by weight of a liquid carrier; and from about 1% to about 60% by weight of a solid, polymorphic, unsubstituted, triglyceride gellant characterized by β′-2 crystalline order within the compositions. These compositions can be formulated as hard sticks, soft solids or creams, and have improved high temperature texture and phase stability and maintain product hardness even after exposure to high and then low storage temperatures.

TECHNICAL FIELD

The present invention relates to antiperspirant stick compositions thatare formulated to contain triglyceride gellants in a stabilizedcrystalline phase characterized by a beta prime-2 (β′-2) crystallineorder.

BACKGROUND OF THE INVENTION

There are many types of solid antiperspirant sticks that arecommercially available or otherwise known in the antiperspirant art.Many of these products contain an antiperspirant active dispersed withina suitable liquid carrier and contained within a solid gellant or waxmatrix that provides the product with sufficient hardness to form asolid antiperspirant stick. In addition to providing sufficient producthardness, the solid gellant or wax matrix also acts to contain theliquid carrier and any other liquid ingredients sufficiently to preventsyneresis of such liquids from the product form prior to application.

Wax gellants such as stearyl alcohol and other fatty alcohols areespecially common in commercially available antiperspirant stickproducts. These waxes typically provide a stable solid matrix withinwhich the antiperspirant active and a liquid carrier can be containedwith minimal or no liquid syneresis during storage. Other gellants suchas the triglyceride gellants have also been used in solid antiperspirantsticks, due in large part to the lower raw material cost associated withthe use of natural triglycerides.

It has been found, however, that antiperspirant sticks that containtriglyceride gellants can develop stability problems after exposure tohigh and then low storage temperatures, which can then result in anundesirable softening of and excessive liquid syneresis from theantiperspirant stick matrix. It has also now been found thattriglyceride-based antiperspirant compositions can be formulated into amore temperature-stable stick form. These compositions are formulated sothat exposure to high and then low storage temperatures does not resultin excessive softening of the product form and also does not result inexcessive development of solvent syneresis during exposure to suchtemperature changes. It has been found that this can be accomplished byformulating the composition with solid polymorphic triglyceridescharacterized by beta prime-2 (β′-2) crystalline order within thefinished product form. It has been found that by formulating thesetriglyceride gellants in this manner, that product stability is improvedsuch that product hardness is better maintained and liquid syneresisminimized, especially when exposed to higher and then lower storagetemperatures.

It is therefore an object of the present invention to provide a solidantiperspirant stick composition that contains a triglyceride gellantand is texture and phase stable when exposed to high and then lowerstorage temperatures. It is a further object of the present invention toformulate such a composition containing a thermodynamically stabletriglyceride gellant, one that is characterized by β′-2 crystallineorder within the finished product form.

SUMMARY OF THE INVENTION

The present invention is directed to anhydrous antiperspirant anddeodorant stick compositions comprising from about 0.1% to about 50% byweight of an antiperspirant or deodorant active; from about 10% to about90% by weight of a liquid carrier; and from about 1% to about 60% byweight of a solid, polymorphic, unsubstituted, triglyceride gellant,wherein the triglyceride gellant within the composition is characterizedby a β′-2 crystalline order.

It has been found that the antiperspirant and deodorant compositions ofthe present invention can be formulated for improved texture and phasestability, wherein the product hardness of the compositions ismaintained after exposure to high and then low storage temperatures. Theimproved stability is made possible within the compositions byformulating the triglyceride gellant into a stable crystalline phasethat is characterized by β′-2 crystalline order within the finishedproduct form. It has been found that antiperspirant and deodorantcompositions containing triglyceride gellants tend to soften whenexposed to high and then low storage temperatures, and that this can beminimized or avoided by formulating the triglyceride gellant into itsβ′-2 crystalline order within the finished product form.

DETAILED DESCRIPTION OF THE INVENTION

The antiperspirant and deodorant stick compositions of the presentinvention comprise as essential ingredients antiperspirant or deodorantactive, a liquid carrier, and a defined crystalline form of apolymorphic triglyceride gellant. Each is described in detailhereinafter.

The term “anhydrous” as used herein refers to those materials orcompositions that contain less than about 5%, more preferably less thanabout 3%, even more preferably less than about 1%, most preferably zeropercent, by weight of free or added water, e.g. water other than thewater of hydration typically associated with some solid materials suchas particulate antiperspirant active.

The term “solid” as used herein, unless otherwise specified, refers tothose materials that are solid at or above 37° C. (skin temperature asmeasured in the axilla area). The term “liquid” as used herein, unlessotherwise specified, refers to those materials that are liquid at orbelow 37° C. As used herein, a material is determined to be a solid or aliquid at 37° C. by evaluating that material in a finishedantiperspirant or deodorant composition using Differential ScanningCalorimetry (DSC). For example, A Perkin Elmer Model DSC-7, manufacturedby Perkin Elmer Corporation, 761 Main Street, Norwalk Conn., can be usedto measure a melting profile of the desired material This is done bypreparing a 20 mg sample in a volatile sample pan arrangement of thedesired finished product to be tested. A heating curve (DSC curve) isgenerated at 5° C. per minute and is analyzed by measuring the partialarea that melts below 37° C. and those showing at least 10% of the DSCcurve below 37° C. are “liquids” and those showing less than 10% of theDSC curve below 37° C. are “solids.”

The term “skin temperature” as used herein refers to the temperature ofthe axilla area of the skin, which is generally at or slightly below atypical body temperature of about 37° C.

The term “ambient conditions” as used herein refers to surroundingconditions under about one (1) atmosphere of pressure, at about 50%relative humidity, and at about 25° C., unless otherwise specified. Allvalues, amounts and measurements described herein are obtained underambient conditions unless otherwise specified.

The term “volatile” as used herein refers to those materials which havea measurable vapor pressure at 25° C. Such vapor pressures willtypically range from about 0.01 mmHg to about 6 mmHg, more typicallyfrom about 0.02 mmHg to about 1.5 mmHg, and have an average boilingpoint at one (1) atmosphere of pressure (atm) of less than about 250°C., more typically less than about 235° C. at one (1) atm. Conversely,the term “non volatile” refers to those materials which are not“volatile” as defined herein.

The antiperspirant and deodorant stick compositions of the presentinvention can comprise, consist of, or consist essentially of theessential elements and limitations of the invention described herein, aswell as any additional or optional ingredients, components, orlimitations known or otherwise effective for use in the suchcompositions.

All percentages, parts and ratios are by weight of the totalcomposition, unless otherwise specified. All such weights as theypertain to listed ingredients are based on the specific ingredient leveland, therefore, do not include solvents, carriers, by-products, filleror other minor ingredients that may be included in commerciallyavailable materials, unless otherwise specified.

Product Hardness

The antiperspirant and deodorant stick compositions of the presentinvention can be formulated as hard sticks, soft solids, creams or otherproduct forms having similar hardness values. The compositions of thepresent invention therefore have a product hardness of at least about100 gram·force, typically from about 100 gram·force to about 5,000gram·force.

For hard stick embodiments, the antiperspirant and deodorant stickcompositions have a product hardness value of at least about 600gram·force, preferably from about 750 gram·force to about 2,000gram·force, more preferably from about 800 gram·force to about 1,400gram·force. For softer product forms such as soft solids or creams, theantiperspirant and deodorant compositions have a product hardness offrom about 100 gram·force to about 600 gram·force, preferably from about120 gram·force to about 500 gram·force, more preferably from about 120gram·force to about 250 gram·force.

The term “product hardness” or “hardness” as used herein is a reflectionof how much force is required to move a penetration cone a specifieddistance at a controlled rate into an antiperspirant stick compositionunder the following test conditions. Higher values represent harderproduct and lower values represent softer product. These values aremeasured at 27° C., 15% relative humidity, using a TA-XT2 TextureAnalyzer, available from Texture Technology Corp., Scarsdale, N.Y.,U.S.A. The product hardness value as used herein represents the peakforce required to move a standard 45° angle penetration cone through thecomposition for a distance of 10 mm at a rate of 2 mm/second. Thestandard cone is available from Texture Technology Corp., as part numberTA-15, and has a total cone length of about 24.7 mm, angled cone lengthof about 18.3 mm, a maximum diameter of the angled surface of the coneof about 15.5 mm. The cone is a smooth, stainless steel construction andweighs about 17.8 grams.

Antiperspirant and Deodorant Active

The antiperspirant and deodorant compositions of the present inventioncomprise an antiperspirant and/or deodorant active suitable forapplication to human skin. The active in the composition may besolubilized or in the form of solid particulates or dispersed liquiddroplets. The concentration of active in the composition should besufficient to provide the desired perspiration wetness and/or deodorantcontrol.

The antiperspirant and deodorant compositions of the present inventionpreferably comprise antiperspirant active at concentrations ranging fromabout 0.1% to about 50%, more preferably from about 5% to about 35%,even more preferably from about 7% to about 30%, by weight of thecomposition. These weight percentages are calculated on an anhydrousmetal salt basis exclusive of water and any complexing agents such asglycine, glycine salts, or other complexing agents.

The antiperspirant active for use in the compositions of the presentinvention include any compound, composition or other material havingantiperspirant activity. Preferred antiperspirant actives includeastringent metallic salts, especially the inorganic and organic salts ofaluminum, zirconium and zinc, as well as mixtures thereof. Particularlypreferred are the aluminum-containing and zirconium-containing salts,such as aluminum halides, aluminum chlorohydrate, aluminumhydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, andmixtures thereof.

Preferred aluminum salts for use in the antiperspirant and deodorantcompositions include those which conform to the formula:

Al₂(OH)_(a)Cl_(b) .xH₂O

wherein a is from about 2 to about 5; the sum of a and b is about 6; xis from about 1 to about 6; and wherein a, b, and x may have non-integervalues. Particularly preferred are the aluminum chlorohydroxidesreferred to as “⅚ basic chlorohydroxide”, wherein a=5, and “⅔ basicchlorohydroxide”, wherein a=4. Processes for preparing aluminum saltsare disclosed in U.S. Pat. No. 3,887,692, Gilman, issued Jun. 3, 1975;U.S. Pat. No. 3,904,741, Jones et al., issued Sep. 9, 1975; U.S. Pat.No. 4,359,456, Gosling et al., issued Nov. 16, 1982; and British PatentSpecification 2,048,229, Fitzgerald et al., published Dec. 10, 1980, allof which are incorporated herein by reference. Mixtures of aluminumsalts are described in British Patent Specification 1,347,950, Shin etal., published Feb. 27, 1974, which description is also incorporatedherein by reference.

Preferred zirconium salts for use in the antiperspirant and deodorantcompositions include those which conform to the formula:

ZrO(OH)_(2−a)Cl_(a) .xH₂O

wherein a is from about 1.1 to about 2.0; x is from about 1 to about 8;and wherein a and x may both have non-integer values. These zirconiumsalts are described in Belgian Patent 825,146, Schmitz, issued Aug. 4,1975, which description is incorporated herein by reference.Particularly preferred zirconium salts are those complexes whichadditionally contain aluminum and glycine, commonly known as ZAGcomplexes. These ZAG complexes contain aluminum chlorohydroxide andzirconyl hydroxy chloride conforming to the above described formulas.Such ZAG complexes are described in U.S. Pat. No. 3,679,068, Luedders etal., issued Feb. 12, 1974; Great Britain Patent Application 2,144,992,Callaghan et al. published Mar. 20, 1985; and U.S. Pat. No. 4,120,948,Shelton, issued Oct. 17, 1978, all of which are incorporated herein byreference.

The antiperspirant and deodorant compositions of the present inventioncan also be formulated with deodorant active in addition to or in placeof the antiperspirant active described hereinbefore. The term “deodorantactive” as used herein includes antimicrobial agents (e.g.bacteriocides, fungicides), malodor-absorbing materials, perfumechemicals that deodorize or mask body odor or which otherwise providethe desired fragrance, or combinations thereof. The concentration ofdeodorant active can vary with the particular active selected, butpreferably ranges from about 0.1% to about 10%, more preferably fromabout 0.1% to about 5%, by weight of the composition.

Preferred deodorant actives are antimicrobial agents, nonlimitingexamples of which include cetyl-trimethylammonium bromide, cetylpyridinium chloride, benzethonium chloride, diisobutyl phenoxy ethoxyethyl dimethyl benzyl ammonium chloride, sodium N-lauryl sarcosine,sodium N-palmethyl sarcosine, lauroyl sarcosine, N-myristoyl glycine,potassium N-lauryl sarcosine, trimethyl ammonium chloride, sodiumaluminum chlorohydroxy lactate, triethyl citrate, tricetylmethylammonium chloride, 2,4,4′-trichloro-2′-hydroxy diphenylether(triclosan), 3,4,4′-trichlorocarbanilide(triclocarban),diaminoalkyl amides such as L-lysine hexadecyl amide, heavy metal saltsof citrate, salicylate, and piroctose, especially zinc salts, and acidsthereof, heavy metal salts of pyrithione, especially zinc pyrithione,zinc phenolsulfate,farnesol, phenoxyethanol, and combinations thereof.Most preferred are triclosan and triclocarban.

Triglyceride Gellant

The antiperspirant and deodorant stick compositions of the presentinvention comprise a solid triglyceride gellant, wherein the solidtriglyceride gellant is characterized by β′-2 crystalline order withinthe composition. Any triglyceride gellant that is known or otherwiseeffective for use in topical products is suitable for use herein,provided that it can also be formulated to have the requisitecrystalline order within the finished product. The concentration of thetriglyceride gellant in the composition ranges from about 1% to about60%, preferably from about 5% to about 30%, even more preferably fromabout 10% to about 26%, by weight of the composition.

The solid triglyceride gellant for use in the composition must be asolid at or above human skin temperature (37° C.), either inherently oras formulated or processed within the finished composition. The solidtriglyceride gellant must also be inherently polymorphic and be capableof being formulated into the composition as a solid matrix that ischaracterized by β′-2 crystalline order as defined herein. Solidtriglyceride gellants that have the above-described characteristics willmost typically be unsubstituted triglycerides or mixtures ofunsubstituted triglycerides that correspond to the following formula:

wherein R1, R2 and R3 are the same or different, and are unsubstitutedhydrocarbon moieties that are preferably in the form of saturated alkylgroups. These triglycerides will most typically be in the form oftriglyceride mixtures wherein R1, R2 and R3 are alkyl groups having from2 to 30 carbon atoms, and wherein the average number of carbon atoms peralkyl group per triglyceride molecule [(R1+R2+R3)/3] ranges from about16 to about 24, more preferably from about 18 to about 22.

These solid, unsubstituted, triglyceride gellants are most typicallyobtained or derived from fully hydrogenated fats such as: (1) vegetablefats and oils such as soybean, corn, sunflower, high erucic acidrapeseed, low erucic acid rapeseed, canola, crambe, meadowfoam,cottonseed, olive, safflower, sunflower, sesame seed, nasturtium seed,tiger seed, ricebran, wallflower, and mustard seed; (2) meat fats suchas tallow or lard; (3) marine oils such as menhaden, pilcherd, sardine,whale or herring; (4) nut fats and oils such as coconut, palm, palmkernel, babassu kernel, or peanut, Chinese Vegetable Tallow; (5)milkfat, butterfat; (6) cocoa butter and cocoa butter substitutes suchas shea, or illipe butter; (7) structured triglycerides fats made fromnatural and synthetic routes; and (8) synthetic triglycerides made fromhydrocarbon sources.

Specific nonlimiting examples of solid, unsubstituted triglyceridegellants suitable for use herein include tristearin, fully hydrogenatedhigh erucic acid rapeseed oil (e.g., HEAR Oil, CanAmera, Canada), fullyhydrogenated CRAMBE oil, and tribehenin (e.g., Syncrowax HR-C, Croda).Most preferred is fully hydrogenated high erucic acid rapeseed oil.

The antiperspirant and deodorant compositions may further comprise othergellant materials in addition to and other than the triglyceridegellants described herein, except that at least about 50%, preferably atleast about 75%, by weight of the total gellant concentration in thecomposition must be the triglyceride gellants as described herein.

The triglyceride gellants as formulated within the compositions of thepresent contain the requisite β′-2 crystalline order, which is athermodynamically stable crystalline phase which does not readily shiftto other crystalline phases over time, even when exposed to higher andthen lower storage temperatures. For purposes of defining thecompositions of the present invention, the crystalline order of thetriglyceride gellant is preferably measured or otherwise characterizedat least about 3 months after formulation, preferably at between about 3and about 6 months after formulation, more preferably at about 6 monthsafter formulation.

The compositions of the present invention remain in the relativelystable β′-2 crystalline phase over periods of time ranging from 0 toabout 12 months, preferably from about 3 to about 12 months afterformulation, more preferably so that the products remain in the β′-2crystalline phase over any time interval thereof, e.g. at any timeinterval between about 3 and about 12 months after formulation. Inmaintaining their intended crystalline form, these compositions alsomaintain their product hardness value at the desired level over the timeintervals listed above, such that the product hardness for the productpreferably does not change by more than about 200 gram·force, morepreferably by not more than about 100 gram·force, as measured at 0 and 6months, more preferably as measured at 3 and 6 months, afterformulation.

The triglyceride gellants within the compositions also remain within thestable β′-2 crystalline phase even after exposure to fluctuating storagetemperatures. In this context, the fluctuating temperatures refer totypical temperature fluctuations during shipping and storage of theantiperspirant and deodorant compositions between various locations andto different climates, e.g., temperature fluctuations most typicallybetween about −17° C. and about 45° C.

Any known or otherwise effective method of formulating or processingtriglyceride solids so that the crystalline phase of the newlyformulated or processed triglyceride solid is characterized by β′-2crystalline order can be applied to the formulation and manufacture ofthe antiperspirant and deodorant compositions of the present invention.Such methods are well known in the edible fat and shortening arts,although it is believed that their reapplication to antiperspirant anddeodorant sticks has not heretofore been described. Examples of suitablemethods are described in greater detail hereinafter.

X-ray Diffraction Methodology

The triglyceride crystalline phase within the antiperspirant anddeodorant compositions of the present invention are characterized byβ′-2 crystalline order. This type of characterization of triglyceridesolids is well known in the chemical and analytical arts, and can beidentified by the x-ray diffraction methodology described hereinafter.

It is well known in the analytical and chemical arts that β′-2crystalline order refers to a particular crystalline phase orcrystalline order for most triglyceride materials. Most triglyceridesare polymorphic materials that can exist within and shift among severaldifferent crystalline phases, including the relatively stable β′-2crystalline order described herein. In this context, beta prime (β′)refers to Orthorhombic crystalline order and can be determined by wellknown x-ray diffraction methods using short spacing measurements.Methods of characterizing the crystalline order of triglycerides foundin high erucic acid rapeseed oil are described in “Polymorphism of1-Behenoyldistearin and 2-Stearoyldibehenin” by E. S. Lutton and A. J.Fehl; Journal of The American Oil Chemists Society, Vol. 49, No5, PP336-337 (1972); and “Structural Analogy Between β′Triacylglycerols andn-Alkanes Toward the Crystal Structure Of β′-2 p.p+2.p Triacylglycerols”by Jacco van de Streek, Paul Verwer, Rene de Gelder, and FrankHollander, JAOCS, Vol. 76, no.11 (1999); which descriptions arcincorporated herein by reference.

As used herein, reference to β′-2 crystalline order includes bothβ_(I)′-2 and β_(II)′-2 behenic-stearic-behenic forms of triglycerides inHEAR oil. The β′ crytalline order is generally characterized by two ormore short spacing reflections in the x-ray powder diagrams around 3.8and 4.2 angstroms. In the context of β′-2, the “2” refers to the longorder characterization of the crystalline phase that is approximatelytwo fatty acid chain lengths long.

The specific characterization of the triglyceride-containing compositionof the present invention as being in a β′-2 crystalline phase isdetermined according to the x-ray diffraction methodology describedhereinafter. The following x-ray equipment is used in the diffractionmethodology: (1) Philips PW1830 HT Generator w/PW1821 Multi-purposeSample Stage, (2) Philips PW1397/60 Theta/2-Theta drive andScintillation Counter, and (3) Philips PW1877 Automated PowderDiffraction Software Program v. 3.5B. Specific instrument parameters areset to divergence slit- ¼°; scatter slit ¼°; mask 10 mm; receiving slit0.05 mm; sample holder 15 mm×20 mm (Philips p/n PW1172); step size 0.05°2-theta; start angle 1° 2-theta; end angle 3° 2-theta; time per step 10sec; anode Cu; generator tension 45 kV; and generator current 40 mA. Tocharacterize short range crystalline order, a scan from start angle 16°2-theta to an end angle of 26° 2-theta is conducted. The β′ crystallineorder is characterized as short spacing reflections around 3.8 and 4.2angstroms.

A external reference standard for use in the methodology is prepared byheating a tribehenin sample (99% tribehenin; Sigma T-7904, Lot# 99H5180)in a 105° C. oven until completely melted. While still molten, themelted tribehenin is then placed in a dewer containing liquid nitrogenuntil completely solid. The solidified tribehenin is ground to a finepowder using a mortar and pestle. The fine tribehenin powder is placedinto a 15 mm×20 mm sample holder (Philips p/n PW1172) and pressed intothe holder using a glass microscope slide. All of the excess sample isremoved using a knife edge. The holder containing the prepared sample,which is now the external reference standard, is then examined to makesure the surface of the sample is flush with the top of the holder priorto obtaining the x-ray diffraction pattern of the newly preparedexternal reference standard.

The composition of the present invention, or any other product forevaluation hereunder, is then prepared for x-ray diffraction analysis,and the results of which are then compared to the x-ray diffractionpattern for the external reference standard. The product or compositionfor analysis is first placed into a 15 mm×20 mm sample holder (Philipsp/n PW1172) and then pressed into the holder using a glass microscopeslide. The holder is then examined to assure that the sample is flushwith the top of the holder prior to obtaining an x-ray diffractionpattern.

X-ray diffraction patterns are obtained for each product sample ofinterest, and then compared and evaluated relative to the x-raydiffraction pattern of the external reference standard describedhereinbefore. The x-ray diffraction patterns are recorded and evaluatedfor each product sample in terms of peak area and height information byimporting the x-ray diffraction patterns of both the external referencestandard and the product sample of interest into a BioRad WinIR softwarepackage, v. 4.14 Level II, assigning a best fit baseline to thecurve(s), integrating the area under the curve(s), and measuring theheight of the curve(s), between 1 and 3 degrees 2-theta.

The triglyceride gellant described herein is characterized by β′-2crystalline order as determined by by the x-ray diffraction analysisdescribed herein. The triglyceride gellant, or product containing thetriglyceride gellant, is considered for purposes of defining thecompositions of the present invention to have the requisite crystallineorder when any one or more of the following x-ray diffractioncharacteristics is noted.

In one embodiment of the antiperspirant and deodorant compositions ofthe present invention, the triglyceride gellant and/or productcontaining the triglyceride gellant is characterized as having β′-2crystalline order by an average AUC (area under the curve) at between 1°and 3° 2-theta that is greater than about 8%, preferably greater thangreater than about 10%, more preferably greater than about 12%, of thecorresponding average AUC for the external reference standard. In thiscontext, the average AUC is determined for the sample product and forthe external reference standard from a 10 sample average, each samplebeing prepared as described herein.

In yet another embodiment of the antiperspirant and deodorantcompositions of the present invention, the triglyceride gellant and/orproduct containing the triglyceride gellant is characterized as havingβ′-2 crystalline order by an average peak height at between 1° and 3°2-theta of greater than about 6%, preferably greater than about 8%, evenmore preferably greater than about 10%, of the corresponding averagepeak height of the external reference standard. In this context, theaverage peak height is determined for the product sample and for theexternal reference standard from a 10 sample average, each sample beingprepared as described above.

It has been found that by formulating these triglyceride-containingcompositions into their β′-2 crystalline phase, that product stabilityis improved such that product hardness is better maintained and liquidsyneresis minimized.

Liquid Carrier

The antiperspirant and deodorant compositions of the present inventioncomprises from about 10% to about 95%, preferably from about 20% toabout 80%, more preferably from about 30% to about 70%, by weight of ananhydrous liquid carrier suitable for topical application.

The liquid carrier preferably comprises a volatile silicone liquid. Theconcentration of the volatile silicone ranges from about 10% to about90%, more preferably from about 15% to about 65%, even more preferablyfrom about 30% to about 60%, by weight of the antiperspirant anddeodorant composition. The volatile silicone may be a cyclic, linear orbranched chain silicone having the requisite volatility as definedherein. Non-limiting examples of suitable volatile silicones aredescribed in Todd et al., “Volatile Silicone Fluids for Cosmetics”,Cosmetics and Toiletries, 91:27-32 (1976), which descriptions areincorporated herein by reference. Preferred among these volatilesilicones are the cyclic silicones having from about 3 to about 7, morepreferably from about 5 to about 6, silicon atoms. Most preferably arethose which conform to the formula:

wherein n is from about 3 to about 7, preferably from about 5 to about6, most preferably 5. These volatile cyclic silicones generally have aviscosity value of less than about 10 centistokes. All viscosity valuesdescribed herein are measured or determined under ambient conditions,unless otherwise specified. Examples of suitable volatile silicones foruse herein include Cyclomethicone D-5 (commercially available from G. E.Silicones); Dow Coming 344, and Dow Corning 345 (commercially availablefrom Dow Corning Corp.); and GE 7207, GE 7158 and Silicone FluidsSF-1202 and SF-1173 (available from General Electric Co.).

Other suitable liquid carriers include non-volatile silicones. Thesenon-volatile silicone carriers are preferably linear and include thosewhich conform to either of the formulas:

wherein n is sufficiently large to render the material non-volatile.These linear silicone materials will generally have viscosity values offrom about 10 centistoke to about 100,000 centistoke, preferably fromabout 10 to about 500 centistoke, more preferably from about 10centistoke to about 200 centistoke, even more preferably from about 10centistoke to about 50 centistoke, as measured under ambient conditions.Examples of non-volatile, linear silicones suitable for use in theantiperspirant and deodorant compositions include Dow Corning 200, DowCorning 225, Dow Corning 1732, Dow Corning 5732, Dow Corning 5750(available from Dow Corning Corp.); and SF-96, SF-1066 and SF18(350)Silicone Fluids (available from G.E. Silicones).

The antiperspirant compositions of the present invention preferablycomprise a combination of volatile and nonvolatile silicone materials,more preferably a combination of volatile and nonvolatile siliconecarrier liquids. Nonlimiting examples of suitable combinations of suchsilicone materials are described in U.S. Pat. No. 5,156,834 (Beckmeyeret al.), which description is incorporated herein by reference.

Other suitable liquid carriers include volatile, nonpolar hydrocarbonliquids. In this context, the term “nonpolar” means that these volatilehydrocarbon liquids have a solubility parameter of less than about 7.5(cal/cm³)^(0.5), most typically about 5.0 (cal/cm³)^(0.5) to less thanabout 7.5 (cal/cm³)^(0.5). These volatile, nonpolar hydrocarbon liquidspreferably contain only hydrogen and carbon and therefore preferablycontain no functional groups. Solubility parameters as described aboveare determined by methods well known in the chemical arts forestablishing the relative polar character of a solvent or othermaterial. A description of solubility parameters and means fordetermining them are described by C. D. Vaughan, “Solubility Effects inProduct, Package, Penetration and Preservation” 103 Cosmetics andToiletries 47-69, October 1988; and C. D. Vaughan, “Using SolubilityParameters in Cosmetics Formulation”, 36 J. Soc. Cosmetic Chemists319-333, September/October, 1988, which descriptions are incorporatedherein by reference.

The nonpolar, volatile hydrocarbon liquid as a liquid carrier for use inthe composition of the present invention is preferably a liquid paraffinand/or isoparaffin having the requisite volatility and nonpolarcharacter. The nonpolar, volatile hydrocarbon liquids can have a cyclic,branched and/or chain configuration, and can be saturated orunsaturated, preferably saturated.

Preferred volatile, nonpolar hydrocarbon liquids are branched chainhydrocarbons having the requisite volatility and solubility parameter,and which have from about 6 to about 40 carbon atoms, preferably fromabout 6 to about 20 carbon atoms. These preferred hydrocarbon liquidswill most typically be formulated as a combination of two or more of theabove-described branched chain hydrocarbons, wherein the combination oftwo or more hydrocarbons have different molecular weights, number ofcarbon atoms, and/or chain configurations. Specific nonlimiting examplesof such combinations include the isoparaffins available from ExxonChemical Company, Baytown, Tex. U.S.A, sold as Isopar M (C13-C14Isoparaffin), Isopar C (C7-C8 Isoparaffin), Isopar E (C8-C9Isoparaffin), Isopar G (C10-C11 Isoparaffin), Isopar L (C11-C13Isoparaffin), Isopar H (C11-C12 Isoparaffin), and combinations thereof.Other nonlimiting examples of suitable branched chain hydrocarbonsinclude Permethyl 99A (C12, isododecane), Permethyl 101A (C16,isohexadecane), Permethyl 102A (C20, isoeicosane), and combinationsthereof. The Permethyl series are available from Presperse, Inc., SouthPlainfield, N.J., U.S.A. Other nonlimiting examples of suitable branchedchain hydrocarbons include petroleum distallates such as those availablefrom Phillips Chemical as Soltrol 130, Soltrol 150, Soltrol 170, andthose available from Shell as Shell Sol-70, -71, and -2033.

Still other suitable isoparaffins include C9-C11 Isoparaffin, C9-C13Isoparaffin, C9-C14 Isoparaffin, C10-C13 Isoparaffin, C12-C14Isoparaffin, C13-C16 Isoparaffin, C14-C18 Isoparaffin, and hydrogenatedpolyisobutene available from Amoco as the Panalane Series and fromFanning Corporation as the Fancor P series.

Nonlimiting examples of other volatile, nonpolar hydrocarbon liquidssuitable for use in the antiperspirant and deodorant compositionsinclude paraffins such as dodecane, octane, decane and combinationsthereof, and the Norpar series of paraffins available from ExxonChemical Company such as Norpar-12, -13, and -15 and the Neosolve seriesof paraffins available from Shell. Yet another example includes C11-C15alkanes/cycloalkanes, such as those available from Exxon as Exxsol D80.

Other suitable liquid carriers for use in the antiperspirant anddeodorant compositions of the present invention include any liquidmaterial suitable for use on human skin which is also compatible withinthe antipersirant and deodorant formulation selected. Examples of someof the many suitable liquid carriers are described in Cosmetics,Science, and Technology, Vol. 1, 27-104, edited by Balsam and Sagarin(1972); U.S. Pat. No. 4,202,879 issued to Shelton on May 13, 1980; andU.S. Pat. No. 4,816,261 issued to Luebbe et al. on Mar. 28, 1989, whichdescriptions are incorporated herein by reference.

Optional Ingredients

The antiperspirant and deodorant compositions of the present inventionmay further comprise any optional materials that are known for use inantiperspirant and deodorant compositions or other personal careproducts, or which are otherwise suitable for topical application tohuman skin.

Nonlimiting examples of such other optional materials include dyes orcolorants, emulsifiers, distributing agents, residue masking agents,inert fillers, pharmaceutical or other topical active, preservatives,surfactants, processing aides such as viscosity modifiers, wash-offaids, and so forth. Other suitable optional materials include othersolid gellants or waxes in addition to and other than the solidtriglyceride gellants described herein. Examples of such optionalmaterials are described in U.S. Pat. No. 4,049,792 (Elsnau); U.S. Pat.No. 5,019,375 (Tanner et al.); and U.S. Pat. No. 5,965,113 (Guskey),which descriptions are incorporated herein by reference.

Methods of Manufacture

The antiperspirant and deodorant stick compositions of the presentinvention may be prepared by any known or otherwise effective technique,suitable for providing an antiperspirant stick composition having theproduct characteristics described herein, provided that the method alsoincludes control over the crystalline phase of the triglyceride gellantso that the triglyceride gellant as formulated into or formed within thecomposition is characterized by the β′-2 crystalline order as describedherein.

Generally, the triglyceride-containing compositions herein can beprepared by controlling or slowing the phase transition of thetriglyceride during formulation as described below and then followingthis with a heat tempering process stage, if necessary, wherein theformulated triglyceride-containing composition comes out of a coolingtunnel stage in the β′-0 crystalline phase (i.e. free of long rangecrystalline order) and then is tempered at 40-45° C. for 3-7 days toinduce the transition to the β′-2 phase. Alternate processing methodsinclude manipulating process cooling temperatures and cooling tunnelconditions to induce the transition to the β′-2 phase. In addition, areheat scraped surface heat exchanger step in the process immediatelyfollowing the cooling heat exchanger may be introduced to acceleratetransition to the β′-2 phase. Finally, seed crystallization in the β′-2phase may be introduced as another method to accelerate transition tothe β′-2 phase.

The antiperspirant and deodorant compositions of the present inventionhave a Percent Delta Texture Value (%DTV) of less than about 15%, whichmeans that the texture and phase stability of the compositions remainssubstanstially stable even when exposed to higher and then lower storagetemperatures. In this context, % DTV (and therefore texture stability)is measured by placing product at 21° C. and other identical product at45° C. Each of the products are maintained at their designated andrespective temperatures for 7 days, and then immediately afterward keptat 21° C. for 7 more days, immediately after which product hardness foreach product is measured and the following texture values calculated:(1) Delta Texture Value (DTV)=Texture Value At 21° C.−Texture Value At45° C. returned to 21° C.; and %DTV=100×DTV/Texture Value at 21° C.

One method of controlling the triglyceride crystalline or molecularphase distribution in a product composition is by controlling the rateof cooling of the liquefied triglyceride solid during formulation sothat the mean DSC (Differential Scanning Calorimetry) for the resultingtriglyceride phase in the formulation is between about 60° C. and about65° C. and the resulting triglyceride gellant in the formulation is inthe β′-2 phase as determined by the x-ray phase methodology describedherein. Methods for determining DSC values for solid materials are wellknown in the chemical arts, and can be easily applied in the presentdevelopment. As an example, a Perkin Elmer model DSC-7 manufactured byPerkin Elmer Corporation, 761 Main Street, Norwalk Conn., can be used tomeasure a melting profile of the desired material This is done bypreparing a 20 mg sample in a volatile sample pan arrangement of thedesired finished product to be tested. The heating curve (DSC curve) isgenerated at 5° C. per minute.

The antiperspirant and deodorant stick compositions of the presentinvention can be formulated by mixing the carrier liquid(s) underambient conditions, or under conditions sufficient to render theadmixture fluid or liquid, and adding the triglyceride and othernon-active solids to the mixture and then heating the resulting mixturesufficiently to liquefy the added materials and to form a single phaseliquid, e.g. 85° C. Antiperspirant solids, if any, are then added to anddispersed throughout the heated, single phase liquid before allowing theresulting combination to cool to approximately 78° C., at which pointperfumes or other similar materials are mixed into the combination,which is then allowed to cool to about 60° C. which is just above thesolidification temperature of the formulation matrix at a cooling rateof from 0.5° C. to 200° C. per minute (rate selected to isolate thetriglyceride gellant in its β′-2 crystalline phase) before being pouredinto dispensing packages and allowed to solidify under ambientconditions, after which the product is tempered at 40° C. to 45° C. toconvert the product if necessary to its β′-2 crystalline order.

The present invention, therefore, is also directed to methods of makingthe antiperspirant and deodorant compositions of the present invention,wherein the compositions are made by any method which controls solidtriglyceride crystallization to the desired end results describedherein.

Method of Use

The antiperspirant and deodorant stick compositions of the presentinvention may be applied topically to the axilla or other area of theskin in an amount effective to treat or reduce perspiration wetnessand/or malodor. The composition is preferably applied in an amountranging from about 0.1 gram to about 20 grams, more preferably fromabout 0.1 gram to about 10 grams, even more preferably from about 0.1gram to about 1 gram, to the desired area of the skin. The compositionsare preferably applied to the axilla or other area of the skin, one ortwo times daily, preferably once daily, to achieve effectiveantiperspirant and malodor control over an extended period.

EXAMPLES

The following non-limiting examples illustrate specific embodiments ofthe antiperspirant and deodorant stick compositions of the presentinvention, including methods of manufacture and use. Each of theexemplified compositions are prepared in a similar manner by combiningthe solid gellants and liquid carriers in a vessel equipped with a heatsource. The combined solids and liquids are heated to a temperatureranging from 85° C. to 96° C. and agitated to dissolve the solidgellants until the mixture forms a homogeneous clear to slightly cloudysolution, at which point the antiperspirant active is added to anddispersed throughout the heated solution while maintaining mixing. Theresulting heated combination is then circulated through a scraped wallheat exchanger and cooled to 62° C. before filling the cooled mixtureinto plastic antiperspirant dispensing canisters and allowed to cool andsolidify within the canisters over a 20 minute period (cooling rate of2° C./min) through a forced air cooling tunnel having an air temperatureof 21° C. The exemplified compositions are then placed in a constanttemperature tempering room maintained at 45° C. for a period of one week(7 days) after which they are withdrawn and returned to room temperaturewhere they are evaluated for hardness and by X-ray crystallography forphase properties according to the method described herein.

Each of the exemplified compositions contain a solid triglyceridecrystalline matrix that is in the β′-2 phase. Additionally, the %DTVvalues are measured and reported within the table 1, exhibit littlechange after exposure to high temperatures. Each of the exemplifiedcompositions is applied topically to the axilla area of the skin, inaccordance with the methods of use described herein.

All exemplified amounts are weight percentages based upon the totalweight of the antiperspirant stick composition, unless otherwisespecified.

TABLE 1 Exam- Exam- Exam- Exam- Ingredient ple 1 ple 2 ple 3 ple 4Example 5 Al Zr Trichlorhydrex 25.00 25.00 20.00 20.00 25.25 GlycinateCyclopentasiloxane 37.375 34.25 42.375 39.25 59.625 Tribehenin 0.00 0.0017.5 20.00 7.50 (Syncrowax HR-C)¹ C18-36 Acid 4.375 5.00 4.375 5.001.875 Triglyceride (Syncrowax HGLC)² Perfume 0.75 0.75 0.75 0.75 0.75C13-14 Isoparaffin 10.00 10.00 10.00 10.00 0 (Isopar M)³ Dimethicone 50cs 5.00 5.00 5.00 5.00 5.00 Fully Hydrogenated 17.5 20.00 0.00 0.00 0HEAR Oil⁴ Totals 100.00 100.00 100.00 100.00 100.00 Product hardness 8851400 725 1185 230 (gram · force) % DTV 5% 3% 8% 6% 4% ¹Croda, Inc., NewYork, New York, USA ²Croda, Inc., New York, New York, USA ³ExxonChemical Company, Baytown, Texas, USA, ⁴CanAmera, Canada

What is claimed is:
 1. Anhydrous antiperspirant and deodorant stickcompositions comprising: (a) from about 0.1% to about 50% by weight ofan antiperspirant or deodorant active; (b) from about 10% to about 90%by weight of a liquid carrier; (c) from about 1% to about 60% by weightof a solid, polymorphic, unsubstituted, triglyceride gellant, whereinthe composition is anhydrous and the triglyceride gellant within thecomposition is characterized by a β′-2 crystalline order.
 2. Thecompositions of claim 1 wherein the stick compositions have a producthardness of at least about 600 gram·force.
 3. The compositions of claim1 wherein the stick compositions have a product hardness of from about100 gram·force to about 600 gram·force.
 4. The composition of claim 1wherein the composition contains less than about 1% by weight of freewater.
 5. The compositions of claim 1 wherein the triglyceride gellantcomprises a solid triglyercide corresponding to the formula:

wherein R1, R2 and R3 are independently selected from saturated alkylgroups having from about 2 to about 30 carbon atoms, and wherein theaverage number of carbon atoms per saturated alkyl group as representedby the expression (R1+R2+R3)/3 is from about 16 to about
 24. 6. Thecomposition of claim 1 wherein the composition comprises from about 5%to about 30% by weight of the solid polymorphic triglyceride gellant. 7.The composition of claim 1 wherein the underarm active is selected fromthe group consisting of antiperspirant actives, antimicrobial agents,perfumes, and combinations thereof.
 8. The composition of claim 7wherein the underarm active is an antiperspirant active selected fromthe group consisting of aluminum-containing active, zirconium-containingactive, and combinations thereof.
 9. The composition of claim 8 whereinthe antiperspirant active within the composition is in the form of solidparticulates.
 10. The composition of claim 1 wherein the triglyceridegellant is selected from the group consisting of tristearin, fullyhydrogenated high erucic acid rapeseed oil, hydrogenated low erucic acidrapeseed oil, CAMBE Oil, tribehenin, and combinations thereof.
 11. Thecomposition of claim 10 wherein the triglyceride gellant is fullyhydrogenated high erucic acid rapeseed oil.
 12. The composition of claim1 wherein the % Delta Texture Value of less than about 15%.
 13. Thecomposition of claim 1 wherein the triglyceride gellant represents atleast about 50% by weight of the total gellant concentration in thecomposition.
 14. The composition of claim 1 wherein the liquid carriercomprises a volatile, nonpolar hydrocarbon liquid.
 15. The compositionof claim 1 wherein the composition contains less than 3% by weight offree or added water.
 16. The composition of claim 1 wherein thecomposition at 6 months after formulation provides an x-ray diffractionpattern according to the X-ray Diffraction Methodology, wherein thepattern is characterized by an average area under the curve at between1° and 3° 2-theta of greater than about 12% of the corresponding averagearea under the curve for a 99% tribehenin external reference standard.17. The composition of claim 1 wherein the composition at 6 months afterformulation provides an x-ray diffraction pattern according to the X-rayDiffraction Methodology, wherein the pattern is characterized by anaverage peak height at between 1° and 3° 2-theta of greater than about10% of the corresponding average peak height of a 99% tribeheninexternal reference standard.
 18. A method of stabilizing antiperspirantand deodorant compositions containing solid, polymorphic, unsubstitutedtriglyceride gellants, wherein the method comprises formulating theantiperspirant and deodorant composition with a triglyceride gellant sothat the within the composition is characterized by β′-2 crystallineorder.